Organic sulphoxides and sulphones and process of preparing them



Patented 20, 1938 UNITED STATES PATENT OFFICE 'onosmosmnoxmss AND S'ULPHONES AND raocsss or PREPARING THEM Harms Uier, Ludwigshai'en-on-the-Rhine, Germany, assignor to I. G. Farbenindustrie Aktiengesellschatt, many Franklort-on-the-Main, Ger- No Drawing. Application June 11, 1935, Serial 10 Claims.

The present. invention relates to organic sulphur compounds and a process of producing same. I

I have found that organic sulphur compounds capable of wide industrial employmentv are obtained by causing alkenyl sulphones or sulphoxides to react with compounds containing at least one nitrogen atom bearing one or more reactive,

hydrogen atoms.

Alkenyl sulphones or sulphoxides are comcontain as substituents any other further atoms or atomic groups, as for example halogens or alkyl, hydroxyalkyl, nitro, hydroxy or carboxylic groups. As compounds containing at least one nitrogen atom bearing at least one reactive hydrogen atom may be mentionedfor example ammonia, primary and secondary alkylamines and hydroxyalkylamines (ethylamine, propylamine, butylamine, octadecylamine, octadecenylamine and monoand di-hydroxyethylamines), primary and secondary aromatic amines (aniline, phenylene diamine, naphthylamine and aminoanthraquinone), monoamines or polyamines of other isocyclic and heterocyclic compounds, aralkylamines, (phenylethylamine) and cycloaliphatic amines (cyclohexylamine) and their mono-N- alkyl, hydroxyalkyl, aryl, aralkyl and acyl compounds. Furthermore.v compounds having at least one NH-group combined in the form'of a ring, as for example piperidine or carbazole, may be employed. The said compounds may also contain halogen atoms, tertiary combined nitrogen atoms or alkyl, hydroxyalkyl, nitro, hydroxyl or carboxylic acid groups.

The reaction usually consists 'of an addition of the unsaturated radicle contained in the s'ulphone employed to the nitrogen-hydrogen r'adicle, the number of radicles being thus added depending on the number of free hydrogen .atoms (chlorbenzene) is frequently of advantage.

In Germany June 15, 1934 employment ofdiluents, such as alcohols (ethyl,

'propyl or benzyl alcohol), ketones (aeetophenone) ethers (dibenzyl ether), hydrocarbons (toluene or xylene), orhalogen hydrocarbons In many cases it is preferable to employ catalysts which favor the reaction. Especially suitable for this purpose are substances having a basic character as for example small amounts of alkali metal or alkaline earth metal oxides, hydroxides, sulphides, carbonates, acetates, phenolates, alcoholates and mercaptides, zinc oxide, cadmium oxide, or substances acting like bases in the present reaction such as salts of zinc or cadmium with organic acids, especially acetic acid, furthermore similar amounts of organic bases such as pyridine or dimethylaniline. The reaction may be carried out at ordinary or increased pressure depending on the boiling point of the initial material or of the diluent.

The compounds obtained may be used for the preparation of dyestufls or, when suitable initial materials are selected, as dyestufis themselves, or as assistants for the textile and related industries or for combating animal or vegetable pests.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 40 of I vinyl-para-tolyl sulphone are heated for from 25 to 30 hours on a waterbath under reflux with 300 parts of 10 per cent aqueous ammonia. After separating the aqueous layer, a yellow oil is obtained which dissolves readily in alcohol and ether and slightly in water. By

adding hydrochloric acid to the alcoholic solution 01' the oil, the hydrochloric acid salt is obtained which, after crystallization from alcohol or water,

Example 2 18 parts of vinyl-paratoly1 sulphone are heated for 6 hours under reflux with .60 parts of piperiinitial materials and probably has the formula:

7 Example 3 18 parts of vinyl-para-tolyl sulphone. 14 parts of beta-naphthylamine and 30 parts of dibenzyl ether are heated under reflux for 10 hours at from 150 to 160 C. When cooled the solution solidifies after some time forming a crystal pulp. The crystals separated fromthe solvent are scarcelysoluble in ligroin, readily soluble in warm alcohol and very readily soluble in benzene, acetone, chloroform, glacial acetic acid, ethyl acetate and pyridine. The resulting base still contains small amounts of unchanged beta-naphthlamine and may be obtained in a pure state by repeated crystallization from alcohol. It melts at 124 C. Analysis gives the composition C19H19NO2S. The constitution of the compound probably corresponds to the formula:

(Ijamomcms 07-0411,.

Similar compounds are obtained for example with carbazole or S-aminoanthrapyrimidine and with other alkenyl sulphones.

Example 4 36 parts of the sodium salt of 1-hydroxy-8- aminonaphthalene-3.6-disulphonic acid are dissolved in 200 parts of water. The solution is adjusted so that it is neutral or at the most only very slightly alkaline to litmus. 19 parts of vinylpara-tolyl sulphone are then added and the whole heated on a boiling water bath for six hours under reflux. After cooling, any unconverted vinylpara-tolyl sulphone is filtered 011 by suction and the aqueous filtrate is evaporated under reduced pressure. The residual mass is dissolved in a little water, hydrochloric acid is added and the resulting precipitate filtered off by suction and extracted with alcohol. The addition compound is thus obtained in a pure form. It is readily soluble in water and may be readily converted for example into its sodium salt.

Other addition compounds of aminohydlroxy compounds -with vinyl sulphones may be obtained in an analogous manner.

Example 5 60 parts of mono-ethyl aniline are heated for 30 hours with 30 parts of vinyl para-tolyl sulphone to about .100" C. The excess mono-ethyl aniline is then distilled off as completely as possible, at a very low pressure and at a temperature of from 160 to 170 C. at the most, and the residue is recrystallized from cyclohexanone. Colorless crystalsare thus obtained which melt at between 71 and 72 C. According to analysis the compound has the formula Cr-zI-IaSNO-z. It is an addition compound of one molecule of each of the initial materials and probably has the formula In a similar manne the addition compounds of vinyl-para-tolyl sulphone and monohydroxyethyl aniline (colorless crystals having a melting point of 88 C.) mono-ethyl-meta-toluidine (colorless crystals melting at 70C.), mono-hydroxyethyl-meta-toluidine (colorless needles melting at between 79 and 80 C.) or other bases, as for example methoxy-5-methyl-N-hydroxyethylaniline, responding to the formula:

NH(CH:CH1OH) CHlO which can be obtained by causing ethylenechlorhydrin to act on 2-methoxy-5-methylaniline at about C. or other derivatives of aniline containing N-oxyalkyl groups, phenylene diamines, diphenylamine, cyclohexylamine, monoalkyl-, alkoxyaryl, aralkyl-cyclohexylamine's and addition compounds with other alkenyl sulphones, can be obtained. I

At higher temperatures, for example at from to C. the reaction generally proceeds more rapidly. If the base employed is difllcultly distillable, any excess of it must be avoided. In this case, it is preferable to add a solvent which can be removed by distillation at a temperature not above 200 C. and to purify the addition compound in another way in order to avoid decomposition while distilling off the unconverted portion of the base.

- Example 6 100 parts of diethylamine are heated for 30 hours with 30 parts of vinyl-para-tolyl sulphone under reflux. After distilling on the excess diethylamine, an oil remains which is purified by dissolving it in alcohol and converting it into the oxalate by addition of a solution of oxalic acid in' alcohol. This salt may be further purified by re-' monoalkyl-beta-naphthylamines, 2-

By introducing a nitro group and reducing it 7 electrically heated'as describedin connection with Fig. l. Numeral II8 designates conduits integral with the upper wall of casing I95 which are connected to high vacuum pumps (not shown) which serve to evacuate the still.

Numeral I29 designates a reservoir provided with a withdrawal and introduction valve I25 and communicates at its base with conduit I26, provided with pump I2!v and valve I29, which serves to deliver distiliand to a flow indicating device I29. Liquid from I29'flows through con' 'duit I38 which delivers it tothe distributing heads .I3I of each vaporizing column. Reference numeral I32 designates holes in the heads III through which the liquid flows onto the heated vaporizing surface of elements II9. A fluid which serves to-cool the walls of the condensing element and'the undistilled residue falling in elements I III and conduits I I2 is introduced through conduit I33 and withdrawnthrough conduit I34.

In operation employing the apparatus of Fig. 1, liquid to be distilled for instance cod-liver oil is introduced through 4I into reservoir I6. Opening H is then closed and high vacuum pumps such as condensation pumps connected to conduits 39 and 49 put into operation. As the pressure in the still is lowered large volumes of gas and volatile materials absorbed in the oil are given oil. De-

gassing is aided by starting pump 56 which withdraws liquid from the reservoir and forces it into distributing head 36, from which it flows in a thin film down the walls of vaporizing element 22,

and falls on to coo i gelement 45. After degassing has been completed and the pressure lowered to an appropriate value for molecular distillation such as about .001 mm., the heating element 22 is heated to an elevated temperature while circulation of the oil is continued. In order to quickly raise the oil to distilling temperature the first portion of element'22 may be heated to a higher temperature than the lower portion by decreasing the resistance of unit 3|.

at about 118 C. which contains vitam n A alco-' rate of flow and temperature of cooling fluid in conduits and GI, then falls into reservoir 'IG and is again re-circulated. Higher boiling fractions are removed at successively elevated temperatures in the-same manner, vitamin D being obtained at about l40-l65 and vitamin A esters at about 180-220 C. v

In order to substantially prevent mixing of dis-,

1 tilled liquid, with undistilled liquid, or with liquid which has been circulated a lesser number of times,reservoir I6 is preferably of considerable length and rather narrow. As a result there is a tendency for liquid falling from the cooling element to stratify and mixing with undistilled liquid is minimized. I This result is made more positive by using the apparatus illustrated in Fig. 2. When using this apparatus, .material to be distilled is introduced into reservoir 66. Valve 61 is closed and the liquid from reservoir 66 circulated through the still in the manner described in connection with Fig. l. Undistilled liquid is .collected in reservoir 66. After reservoir 66 has reached a desired low value valve 61 is opened and the contents of allowed to flow into 66. The valve is again closed and the re-circulation continued. The use of the system of reservoirs prevents any possibility of mixing and also enables theexact time of an individual cycle to be measured by the time taken to empty the reservoir. Since the rate of distillation under molecular conditions is proportional to the mo]. fraction of the material to be removed from the distilland it is desirable to prevent-mixing of dis-' tilled material poor in'the substance to be separated, with richer undistilled material, or material which has beenthrough the still a lesser number of times. 7

The operation of the apparatus illustrated in Figs. 6 and '1 is practically the same as' that of Fig. 1 except that liquid to be distilledis cir. culated over a plurality of heated vaporizing elements. Instead of air cooling the condenser walls cooling is eil'ected by circulating cooling fluid such as water through conduits I33 and I34. Since this cooling fluid is also in contact with conduits.

H2 and flared members IIII, undistilled liquid is cooled as it falls from the vaporizing elements and is conveyed to the reservoir.

In operation employing the apparatus of Figs. 3, 4.and 5, liquid to be distilled is introduced into reservoir 9i through valve 98. Vacuum pumps connected to" and I5 are started and liquid drawn from 9i by pump 96 and forced'into conduits I6. The liquid flows through the small perforations 11 in the bottom of conduits I6 and falls. on heating elements 19 which may be warmed to improve the rate of degassing. The lquid falls from elements 19 into gutters 89 and flows through perforations 88, down the cooled walls 84 on to slanted plate II which collects and returns it to reservoir 9| by way of conduit 90. ments I9 are heated to the distilling temperature of the first fraction and re-cycling continued 'until it has been removed. Distillate condensing onplates 94 and walls III drops onto slanted plate 62 which also acts as a condenser and is delivered iilm and prevent its gathering in local streams.

Itwill be apparent that many changes can be made in the above described structures or in their specific mode of operation without departing from the spirit or scope of my invention, For instance while I have disclosed the apparatus as being equipped with cooling elements it is apparent that in distilling relatively stable compounds such coolingwould be unnecessary. In distilling materials oi. low stability, such as vita- After degassing has been completed elemin containing fails, it is important that the contents of the reservoir be below that at which decomposition takes place. The use of cooling elementsin such a case is therefore advisable. Instead of using internal vaporizing elements it may be desirable to flow the distilland down a heated external surface and condense distillate upon a smaller centrally located cooled surface. By thus reversing the positions of the vaporizing and condensing surfaces, the condensate is collected upon a smaller area and its rate of drainage thus increased. The number, shape and size of the vaporizing elements can obviously be varied considerably, to conform with the requirements of any particular distillation treat ment. By varying the size and length of these elements and the rate of flow of distilland any desired heating period can be obtained. Preferred dimensions are those which enable a short heating period. Thus short columns or heating conduits of relatively small diameter and rapid cooling of undistilled residue lessen the possibility of thermal decomposition.

The essential operating conditions for molecular distillation process are well known. and have been described by Burch U. S. Patent 1,955,321; Hickman U. S. Patents 1,942,858, and 1,925,559; Carr British Patent 415,088; Washburn, Bur. St.,Jour. Res." 2 478-83 (1929) Carr et al. Nature 131 92 (Jan. 21, 1933) and Bronsted et al. "Philosophical Magazine 43 31-49 (1922). Pressures below .1 mm.-and preferably below .01 mm. such as between .001 and .0001 mm. are usually employed. Distances separating the evaporating and condensing surfaces maybe up to twice the mean free path of residual gas. However distances of less than the mean free path give considerably faster distillation rates and are therefore generally used. As the path increases with decrease in pressure there is no limit to the distance which may be employed as long as the pressure used is sufficiently low for the particular distance selected.- Usually. distances of up to 10 inches such as between k and 6 inches have been found to be most satisfactory. Temperatures of between room temperature and 350 C. may be employed. Those temperatures between 50 and 300 C. and especially between 70 and 250 C.

. are most satisfactory for distilling animal and molecular they are to be understood as being within the scope of my' invention.

While I have found it convenient to describe my invention by reference to the'distillation of particular materials it is broadly applicable to the distillation ofall substances amenable. to high vacuum distillation, such as hydrocarbons, drying oils, animal and vegetable glycerides, fats and waxes, etc. MLv inventionis of special value in the molecular distillation of vegetable and animal oils such as cottonseed, tima-liver, wheat germ, menhaden, halibut-liver, salmon and other fish oils, linseed etc., oils, to obtain fat soluble vitamin concentrates or purified highly unsaturated gl'ycerides.

By operating in accordance with my invention it-is possible to regulate and change the distillation to an extent heretofore unattainable. Due

to the facility with which distillation conditions can be regulated my invention enables avoidance of overheating or underheating and attendant loss in distillation rate or decomposition. In distilling fish oils 'it has been found that by using apparatus of the type described, that a much higher yield of vitamin concentrates is obtained tillates from the conventional still, apparentlybecause of complete destruction. 1 It is therefore seen that due to the possibility of careful regulation and short heating period that thermal decomposition is avoided to a considerable extent. Although degassed distilland may be used my invention has the decided advantage that untreated oil may be introduced into the still and the degassing and distillation carried out therein in one treatment. An outstanding advantage of my invention is that fractionation under molecular conditions can be performed without using a series of stills thus greatly decreasing the pieces of apparatus required and eliminating expense and difllculties associated with their operation.

It is to be understood the term high vacuum as used in the specification and claims is to be accorded its common meaning in the vacuum art,

namely, a pressure of the order of .1 mm. or less.

What I claim is: s

1. Distillation apparatus comprising in a closed system a vaporizing surface,- a condensing surface disposed opposite thereto in such a. manner that free unrestricted space is available for travel of vaporized molecules from the evaporating to the condensing surface, means for maintaining a high vacuum in the space between said surfaces, means for continuously conveying distilland onto the vaporizing surface and means located within v the still for quickly cooling undistilled liquid, to below decomposition temperature as it is removed from the vaporizing surface- 2. Distillation apparatus comprising in a closed system a vaporizing surface, a condensing surface disposed in such relation thereto that unrestricted space is available for travel of vaporized molecules from the vaporizing to the condensing surface, means for maintaining a high vacuum in the space between the surfaces, a. reservoir for material to be distilled, means for withdrawing material from the reservoir and introducing it onto the evaporating surface and means for immediately cooling undistilled material to below decomposition temperature and returning it to the reservoir.

3. Distillation apparatus comprising in a closed system a vaporizing surface, a condensing surface disposed in such relation thereto that unrestricted space is available for travel of vaporized molecules from the vaporizing to the condensing surface, a reservoir for material to be distilled,

means for maintaining a high vacuum over the tion temperature, and returning it to the reser- 75,

between about 60 and about 200 c. a compound of the general formula RX-Ri in which x stands for a group selected from the class consisting of --SO and S02, R for an alkenyi group-containing up to 3 carbon atoms and R1 for a radicle'of the group consisting of aliphatic and cyclo-aliphatic radicles containing at least 6 Alkyl CH C H4 S01 CjHlN Alkyl 7. The organic sulphur compound having the formula CHa.CoH4.SO:.C2H4.N(C2Hs) v 8. Organic sulphurcompounds corresponding to the general formula in which A stands for an alkyl group containing at least 12 carbon atoms, X for a group selected from the class consisting of SO and -SO: and Y for a member of the group consisting of hydrogen and alkyl groups.

9. The organic sulphur compound having the formula C||Har'SOCHr-CH;N a

CHr-CHi-BOaH 10. Organic sulphur compounds corresponding to the general formula RiXCH:-CHY-Z, in which R1 stands for a radicle oi the group consisting of aliphatic and cycloaliphatic hydrocarbon radicles containing at least 6 carbon atoms, aliphatic-aromatic and aromatic hydrocarbon radicies of the benzene and naphthalene series, X stands for a group selected from the class consisting of SO-- and SO ,Y stands for a member of the group consisting of hydrogen and the methyl group, and Z stands for a member selected from the group consisting of the primary and sec-.

ondary mono-amines-and secondary heterocyclic bases. the amino nitrogen atom of which is attached to the carbon atom of the grouping CHY.

' I v HANNS UFER. 

